Certain propene derivatives as intermediates for the preparation of pesticidal silane derivatives

ABSTRACT

New propene derivatives as intermediates for the preparation of pesticidal silane derivatives. Compounds of the formula ##STR1## wherein R 4  is H, R 5  is a radical of the formula ##STR2## and R 17  is H or halogen are useful intermediates for the preparation of pesticidal silane derivatives.

This application is a division of application Ser. No. 211,155which is acontinuation of Ser. No. 922,734, filed on Oct. 24, 1986, now abandoned,filed June 22, 1988 now U.S. Pat. No. 4,864,027.

The basic structures known hitherto of insecticidal, acaricidal andnematocidal active compounds include such differing groups of substancesas, for example, the phosphoric acid derivatives, thechlorohydrocarbons, the N-methylcarbamates, the cyclopropanecarboxylatesand the benzoylureas, to mention just a few of the most important.Amazingly, however, (with a single exception, see Japanese PublishedSpecification No. 60/123,491) no insecticidal, acaricidal andnematocidal compounds which contain a basic structure containing theelement silicon have hitherto been described (C. Worthing, The PesticideManual, 7th edition, Lavenham 1983; S. Pawlenko,Organo-Silicium-Verbindungen [Organosilicon Compounds] in: Methoden derorg. Chemie [Methods of Organic Chemistry] (Houben-Weyl), Volume XIII/5,Georg Thieme Verlag, Stuttgart 1980; R. Wegler, Chemie derPflanzenschutz- und Schadlingsbekampfungsmittel [The Chemistry ofPlant-Protection Agents and Pesticides], Vols. 1, 6 and 7,Springer-Verlag, Berlin 1970, 1981). The same fact applies to theherbicide sector, and fungicide research has also only led to one casehitherto of the discovery of a silicon-containing basic structure fortriazol fungicides (EP-A No. 68,813).

Novel active compounds having a silicon-containing basic structure havenow been found which have advantageous applicational properties in thearea of the insecticides, acaricides and nematocides.

The present invention thus relates to the compounds of the formula (I),the various optical isomers, and their possible mixtures, ##STR3##wherein X denotes CH₂, O, S or NR⁶,

R¹ denotes (C₂ -C₁₈)alkyl, (C₅ -C₇)cycloalkyl, (C₂ -C₈)alkenyl, phenylor naphthyl, all these substituents being optionally mono- orpoly-substituted, with the exception of pentafluorophenyl,

R² and R³, independently of one another, denote (C₁ -C₃)alkyl, (C₂-C₈)alkenyl, or phenyl, or R² and R³ together denote an alkylene chainwhich--together with the silicon atom--produces an unsubstituted or (C₁-C₄)alkyl-substituted heterocycle having 4 to 6 ring members,

R⁴ denotes --H, --CN, --CCl₃, --C.tbd.CH, (C₁ -C₄)alkyl, F or ##STR4##R⁵ denotes pyridyl, furyl or thienyl, which can all be substituted,phthalimidyl, di(C₁ -C₄)alkylmaleinimidyl, thiophthalimidyl,dihydrophthalimidyl, tetrahydrophthalimidyl, or substituted phenyl withthe exception of 4-acetylphenyl, 2-chlorophenyl and4-ethoxycarbonylacetylphenyl or

R⁴ and R⁵ --together with the carbon atom bridging them--denote anoptionally substituted indanyl, cyclopentenoyl or cyclopentenyl radical,and

R⁶ denotes H, (C₁ -C₃)alkyl or phenyl, with the proviso that thecompounds of the formula (I) in which

R¹ denotes phenyl which is substituted in the paraposition by (C₁-C₄)alkoxy, halogen or (C₁ -C₄)alkyl;

R² and R³ denotes CH₃ ; X denotes O; R⁴ denotes H, and

R⁵ denotes 3-phenoxyphenyl or (4-fluoro-3-phenoxy)phenyl are excluded.

Optionally substituted alkyl for R¹ preferably represents (C₂ -C₁₂)alkylwhich may be substituted by halogen or (C₁ -C₄ alkoxy. Examples whichmay be mentioned as optionally substituted ethyl, n-propyl, i-propyl,n-butyl, t-butyl, 3,3-dimethylbutyl, n-octyl, n-decyl, n-dodecyl andn-octadodecyl.

Optionally substituted cycloalkyl for R¹ preferably representsoptionally mono- or disubstituted cyclohexyl, preferred substituentsbeing C₁ -C₄)alkyl, halogen and C₁ -C₄)alkoxy.

Optionally substituted alkenyl for R¹ preferably represents (C₄-C₈)alkenyl which can be mono- or polysubstituted by halogen and/ormono- or disubstituted by (C₁ -C₄)alkoxy. Examples which may bementioned are optionally substituted 3-butenyl, 5-hexenyl and 7-octenyl.

Optionally substituted phenyl or naphthyl for R¹ preferably represent aphenyl or naphthyl radical of the general formula (A) or (B), ##STR5##in which 0≦m+n+o≦4 and

m, n and o can have the values 0 to 4 in the case of formula (A) or 0 to3 in the case of formula (B).

R⁷, R⁸ and R⁹, independently of one another, represent optionallyhydroxy-substituted (C₁ -C₄)alkyl, tri(C₁ -C₄)alkylsilyl, halogen,nitro, cyano, (C₂ -C₆)alkenyl, (C₂ -C₆)alkinyl, amino, (C₃-C₇)cycloalkyl, phenyl, phenoxy, (C₁ -C₅)alkoxy, (C₂ -C₄)alkenyloxy, (C₂-C₄)alkinyloxy, hydroxycarbonyl, (C₁ -C₄)alkylthio, (C₃-C₇)cycloalkyloxy, (C₁ -C₆)alkylcarbonyl, (C₁ -C₄)alkoxycarbonyl, (C₂-C₄)alkenyloxycarbonyl, (C₃ -C₅)alkinyloxycarbonyl, (C₁ -C₄)haloalkyl,(C₁ -C₄)alkoxy(C₁ -C₄)alkyl, (C₁ -C₃)haloalkoxy, (C₁ -C₃)-haloalkylthio,halo(C₁ -C₄)alkoxy(C₁ -C₄) alkyl, (C₁ --C₄)alkylthio(C₁ --C₄)alkyl, (C₁-C₄)alkoxy(C₁ -C₄)alkoxy, halo(C₁ -C₄)alkoxy(C₁ -C₄)alkoxy, (C₂-C₄)-alkenyloxy(C₁ -C₄)alkoxy, halo(C₂ -C₄)alkenyloxy, (C₁ -C₄)alkoxy(C₁-C₄)alkylthio, (C₁ -C₄)alkylthio(C₁ -C₄)alkoxy, (C₁ -C₄)alkylthio(C₁-C₄)alkylthio, halo(C₁ -C₄)alkoxycarbonyl, halo(C₂-C₄)alkenyloxycarbonyl or di(C₁ -C₆ alkyl)amino, or two of the radicalsR⁷ , R⁸ and R⁹, if they are in the ortho-positions to one another, forma methylenedioxy, ethylenedioxy or (C₃ -C₅)alkylene radical.

R⁷, R⁸ and R⁹ preferably denote halogen, (C₁ -C₄)alkyl, (C₂ -C₆)alkenyl,(C₃ -C₇)cycloalkyl, (C₁ -C₅)-alkoxy, (C₂ -C₄)alkenyloxy, (C₁-C₄)haloalkyl or (C₁ -C₃)haloalkoxy.

The radical R¹ preferably denotes the phenyl radical which has 0-3substituents from the selection specified for R⁷ -R⁹. Particularlypreferred phenyl radicals are those having 1-3, particularly having 1-2,substituents in the m- or p-position, selected from the radicals R⁷ -R⁹described above, halogen, (C₁ -C₄)alkyl, (C₁ -C₄)haloalkyl, (C₁-C₃)haloalkoxy and (C₁ -C₅)-alkoxy being preferred. Specific examples ofthe radical R¹ are listed below, although the radicals R¹ coming withinthe scope of the invention are not limited to those which are mentionedas examples.

The following are mentioned as specific examples of R¹ : ethyl,n-propyl, i-propyl, n-butyl, 3,3-dimethylbutyl, n-octyl, n-decyl,n-octadecyl, cyclohexyl, benzyl, 5-hexenyl, 7-octenyl, 1-naphthyl,phenyl, 3-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl,4-chlorophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl,2-naphthyl, 3,4-dichlorophenyl, 4-nitrophenyl, 4-methylthiophenyl,4-methoxyphenyl, 3,4-dimethoxyphenyl, 3,4-methylenedioxyphenyl,4-difluoromethylthiophenyl, 4-trifluoromethylthiophenyl,3,4-difluoromethylenedioxyphenyl, 4-cyanophenyl, 4-fluorophenyl,4-bromophenyl, 3,4-difluorophenyl, 3,4-dibromophenyl,4-chloro-3-fluorophenyl, 3-chloro-4-fluorophenyl,3-chloro-4-methylphenyl, 3-bromo-4-chlorophenyl,4-difluoromethoxyphenyl, 3,4-bis(difluoromethoxy)phenyl,4-trifluoromethoxyphenyl, 3,4-bis(trifluoromethoxy)phenyl,4-methoxy-3,5-dimethylphenyl, 3,4-trifluoroethylenendioxyphenyl,4-tert.-butylphenyl, 4-ethylphenyl, 4-isopropylphenyl,3,4-difluoroethylenedioxyphenyl, 4-isopropenylphenyl, 4-vinylphenyl,4-(2,2-dichlorovinyl)phenyl, 4-chloro-3-methylphenyl,3-bromo-4-fluorophenyl, 3-fluoro4-bromophenyl, 4-fluoro-3-methylphenyl,3-fluoro-4-methylphenyl, 3-bromo-4-methylphenyl, 3,4-diethylphenyl,3,4-diisopropylphenyl, 3-ethyl-4 -methylphenyl,4-isopropyl-3-methylphenyl, 4-methylsulfoxyphenyl, 4-allylphenyl,4-acetylphenyl, 4-carbethoxyphenyl, 4-ethoxyphenyl,1,2,3,4-tetrahydronaphthalene-7-yl, 3,5-dichloro-4-methylphenyl,indane-5-yl, 4-propargylphenyl, 3-methoxy-4-methylphenyl,4-methoxymethylphenyl, 4-(1-chloroethylene-1-yl)phenyl,4-(2-chloroallyl)phenyl, 4-isobutyrylphenyl, 4-methoxycarbonylphenyl,3-nitro-4,5-dimethylphenyl, 3-ethoxy-4-bromophenyl,3-chloro-4-methoxyphenyl, 4-bromo-3-chlorophenyl,3,4-(di-tert.-butyl)phenyl, 4-ethyl-3-methylphenyl,4-tert.-butyl-3-methylphenyl, 4-(1,1,2,2-tetrafluoroethoxy)phenyl,4-(2,2-dichlorovinyloxy)phenyl, 4-(2,2,2-trifluoroethoxy)phenyl,4-pentafluoroethoxyphenyl, 4-(chlorodifluoromethoxy)phenyl,4-(chlorofluoromethoxy)phenyl, 4-(dichlorofluoromethoxy)phenyl,4-(1,1-difluoroethoxy)phenyl,4-(1,2,2-trichloro-1,2-difluororethoxy)phenyl,4-(2-bromo-1,1,2,2-tetrafluoroethoxy)phenyl, 4-(2-propynyloxy)phenyl,4-(1-propynyloxy)phenyl, 4-allyloxyphenyl, 4-ethinyloxyphenyl,4-(2-chloroethinyl)phenyl, 4-(n-propoxy)phenyl, 4-isopropoxyphenyl,4-cyclopentyloxyphenyl, 4-(n-amyloxy)phenyl, 4-isobutoxyphenyl,4-iodophenyl, 4-vinyloxyphenyl, 4-biphenyl, 4-(n-butoxy)phenyl,4-(sec.-butoxy)phenyl, 6-methyl-2-naphthyl, 4-phenoxyphenyl,4-(2-iodo-1,1-difluoroethoxy)phenyl, 4-cyclohexyloxyphenyl,3-chloro-4-ethoxyphenyl, 4-formylphenyl, 4-ethoxymethylphenyl,4-trifluoroacetyloxyphenyl, 4-(1-methoxyethyl)phenyl,4-(1-ethoxyethyl)phenyl, 4-ethoxy-3-methylphenyl,4-(2-methylpropenyl)phenyl, 4-(1,2,2-trifluorovinyloxy)phenyl,3,4-diethoxyphenyl, 4-ethinylphenyl, 4-ethoxy-3,5-dimethylphenyl,4-ethoxy-3-methoxyphenyl, 4-ethylthiophenyl,4-(2,2,2-trifluoroethoxycarbonyl)phenyl, 4(2-chloroethoxy)phenyl,4-(1-buten-2-yl)phenyl, 4-(2-buten-2-yl)phenyl,4-methoxymethylthiophenyl, 4-(1,2-dichlorovinyloxy)phenyl,4-(2,3-dichloroallyloxy)phenyl, 4-(2-iodo-1-fluorovinyloxy)phenyl, 4-(2-(fluoroethoxy)phenyl, 4-(2-chloro-1,1-difluoroethoxy)phenyl,4-(2-chloro-1-fluorovinyloxy)phenyl, 4-isopropylthiophenyl,4-(2,2-dichloro-1,1difluoroethoxy)phenyl,4-(2,2-dichloro-1-fluorovinyloxy)phenyl,4-(1,1,2,2-tetrafluoroethoxy)phenyl, 3-chloro-4-ethoxyphenyl,4-(tetrahydro-3-furyloxy)phenyl, 4-ethylthio, 3-ethoxyphenyl,4-allyloxyphenyl, 4-methoxymethylthiophenyl,4-(2,2-dichlorovinyloxy)phenyl and 4-(1,1,1-trifluoroethoxy)phenyl.

R² and R³ preferably represent a (C₁ -C₃)alkyl radical such as methyl,ethyl, i-propyl or n-propyl, or

R² and R³ together form an alkylene chain which--together with thesilicon atom--produces a four- to six-membered ring such as, forexample, silacylobutane, silacyclopentane or silacyclohexane.

R⁴ preferably represents hydrogen, cyano or (C₁ -C₄)alkyl, butparticularly preferably for hydrogen.

R⁵ in a substituted phenyl, preferably represents a phenyl radical ofthe general formula (C), ##STR6## in which R¹⁰ and R¹¹ --independentlyof one another--may denote H, halogen, (C₁ -C₄)alkyl, (C₁ --C₄)alkoxy,(C₁ -C₄)haloalkyl, phenyl, N-pyrrolyl or a group of the general formula(D) ##STR7## in which R¹² and R¹³ --independently of one another--mayagain denote H, halogen, (C₁ -C₄)alkyl, (C₁ -C₄) alkoxy or (C₁-C₄)haloalkyl.

U represents --CH₂ --, >C═O, --O-- or --S--, but preferably --O--;

V and W represent CH or N, where both may simultaneously denote CH;however, where V represents N, W represents CH, and vice versa.

Furthermore, the following is valid regarding formulae (C) and (D):

p, q denote an integer from 0 to 5, with the condition that the sum p+qmust denote a number from 1 to 5,

r, s denote 0, 1 or 2, with the condition that the sum of r+s must be 0,1 or 2, and with the condition that, if R¹⁰ or R¹¹ corresponds to thegroup (D),

p and q must denote 0 or 1 and p+q must denote 1 or 2. Of these radicalsfor R⁵, radicals of the formula (C) in which (R¹⁰)_(p) denotes H or4-fluoro, and (R¹¹)_(q) is located in the 3-position of the phenylradical and denotes the radical ##STR8## are of particular importance.R⁵ in optionally substituted pyridyl represents a monosubstitutedpyridyl group of the general formula (E), ##STR9## in which R¹⁴ denoteshalogen, apart from I, (C₁ -C₄)alkyl, (C₁ -C₄)alkoxy or (C₁-C₄)haloalkyl and Hal denotes halogen, particularly fluorine, or H.

R⁵ in optionally substituted thienyl or furyl represents a heterocycleof the general formula (F), ##STR10## in which Z denotes O or S,

R¹⁵ denotes H, halogen, (C₁ -C₄)alkyl, (C₁ -C₄)alkoxy, (C₁-C₄)haloalkyl, CN or NO₂, and

R¹⁶ denotes optionally substituted benzyl, propargyl or allyl.

Substituted phenyl radicals for R⁵ are of particular importance for theinvention.

The following radicals are specified as typical examples of the group R⁵:

pentafluorophenyl, 5-benzyl-3-furyl, 4-phenoxyphenyl, 3-phenoxyphenyl,3-(4-fluorophenoxy)phenyl, 3-(4-chlorophenoxy)phenyl,3-(4-bromophenoxy)phenyl, 3-(3-fluorophenoxy)phenyl,3-(3-chlorophenoxy)phenyl, 3-(3-bromophenoxy)phenyl,3-(2-fluorophenoxy)phenyl, 3-(2-chlorophenoxy)phenyl,3-(2-bromophenoxy)phenyl, 3-(4-methylphenoxy)phenyl,3-(3-methylphenoxy)-phenyl, 3-(2-methylphenoxy)phenyl,3-(4-methoxyphenoxy)phenyl, 3-(3-methoxyphenoxy)phenyl,3-(2-methoxyphenoxy)phenyl, 3-(4-ethoxyphenoxy)phenyl,3-(phenylthio)phenyl, 3-(4-fluorophenylthio)phenyl,3-(3-fluorophenylthio)phenyl, 3-benzoylphenyl, 3-benzylphenyl,3-(4-fluorobenzyl)phenyl, 3-(4-chlorobenzyl)phenyl,3-(3,5-dichlorophenoxy)phenyl, 3-(3,4-dichlorophenoxy)phenyl,3-(4-chloro-2-methylphenoxy)phenyl, 3-(2-chloro-5-methylphenoxy)phenyl,3-(4-chloro-5-methylphenoxy)phenyl, 3-(4-ethylphenoxy)phenyl,3-(3-chloro-5-methoxyphenoxy)phenyl, 3-(2,5-dichlorophenoxy)phenyl,3-(3,5dichlorobenzoyl)phenyl, 3-(3,4-dichlorobenzoyl)phenyl,3-(4-methylbenzyl)-phenyl, 3-(4-isopropoxyphenoxy)phenyl,4-fluoro-3-phenoxyphenyl, 4-chloro-3-phenoxyphenyl,4-bromo-3-phenoxyphenyl, 4-fluoro-3-(4-fluorophenoxy)phenyl,4-fluoro-3-(4-chlorophenoxy)phenyl, 4-fluoro- 3-(4-bromophenoxy)phenyl,4-fluoro-3-(4-methylphenoxy)phenyl, 4-fluoro-3-(4-methoxyphenoxy)phenyl,4-fluoro-3-(3-fluorophenoxy)phenyl, 4-fluoro-3-(3-chlorophenoxy)phenyl,4-fluoro-3-(3-bromophenoxy)phenyl, 4-fluoro-3-(3-methoxyphenoxy)phenyl,4-fluoro-3-(4-ethoxyphenyl)phenyl, 4-fluoro-3-(2-fluorophenoxy)phenyl,3-methoxy-5-phenoxyphenyl, 2-fluoro-3phenoxyphenyl,2-fluoro-3-(4-fluorophenoxy)phenyl, 2-fluoro-3-(3-fluorophenoxy)phenyl,2-fluoro-3-(3-fluorophenoxy)phenyl, 2-fluoro-3-(2-fluorophenoxy)phenyl,3-fluoro-5-(4-fluorophenoxy)phenyl, 3-fluoro-5-(fluorophenoxy)phenyl,3-fluoro-5-(2-fluorophenoxy)phenyl, 4-methyl-3-phenoxyphenyl,3-fluoro-5-(4-methylphenoxy)phenyl, 3-fluoro-5-(3-methoxyphenoxy)phenyl,2-fluoro-5-(4-fluorophenoxyl)phenyl, 2-fluoro-5-(3-fluorophenoxy)phenyl,2-fluoro-5-(2-fluorophenoxy)phenyl, 2-chloro-3-phenoxyphenyl,3-fluoro-5-phenoxyphenyl, 2-fluoro-5-phenoxyphenyl,2-chloro-5-phenoxyphenyl, 2-bromo-5-phenoxyphenyl,4-chloro-3-(3-methylphenoxy)phenyl, 4-chloro-3-(4-fluorophenoxy)phenyl,3-chloro-5 -phenoxyphenyl, 3-bromo-5-phenoxyphenyl,4-bromo-3-phenoxyphenyl, 4-trifluoromethyl-3-phenoxyphenyl,4-fluoro-3-phenylthiophenyl, 4-fluoro-3-benzylphenyl,3-(2-pyridyloxy)phenyl, 3-(3-pyridyloxy)phenyl,4-fluoro-3-(2-pyridyloxy)phenyl, 4-chloro-3-(2-pyridyloxy)phenyl,4-bromo-3-(2-pyridyloxy)phenyl, 4-methyl-3-(2-pyridyloxy)phenyl,4-fluoro-3-(3-pyridyloxy)phenyl, 4-chloro-3-(3-pyridyloxy)phenyl,4-bromo-3-(3-pyridyloxy)phenyl, 4-methyl-(3-pyridyloxyphenyl),2-methyl-3-phenylphenyl, 2-methyl-(N-pyrrolyl)phenyl,6-phenoxy-2-pyridyl, 6-(4-fluorophenoxy)-2-pyridyl,6-(4-chlorophenoxy)-2-pyridyl, 6-(4-bromophenoxy)-2-pyridyl,6-(4-methylphenoxy)-2-pyridyl, 6-(4-methoxyphenoxy)-2-pyridyl,6-(4-ethoxyphenoxy)-2-pyridyl, 6-(3-fluorophenoxy)-2-pyridyl,6-(3-chlorophenoxy)-2-pyridyl, 6-(3-bromophenoxy)-2-pyridyl,6-(3-methoxyphenoxy)-2-pyridyl, 6-(2-fluorophenoxy)-2-pyridyl,6-(2-chlorophenoxy)-2-pyridyl, 6-(2-bromophenoxy)-2-pyridyl,5-propargyl-3-furyl, N-phthalimidyl, N-3,4,5,6-phthalimidyl, 2-methyl-5-propargyl-3-furyl, 4-t-butylphenyl, 4-methylphenyl,4-isopropylphenyl, 4-(2-chloro-4-trifluoromethyl-2-pyridyloxy)phenyl,4-cyclohexylphenyl, 4-difluoromethoxyphenyl, 4-biphenylyl and4-trimethylsilylphenyl.

Further typical examples of the group ##STR11## are:2-allyl-3-methylcyclopent-2-en-1-one-4-yl and 4-phenylindane-2-yl.

The present invention also relates to processes for the preparation ofthe compounds of the general formula (I) wherein

(a) for compounds having X=CH₂, a silane of the general formula (II),##STR12## in which Y denotes a nucleofugic leaving group such as, forexample, halogen or sulfonate, is reacted with an organo-metallicreagent of the general formula (III), ##STR13## in which M correspondsto an alkali metal or alkaline earth metal, particularly Li, Na, K, orMg,

X' corresponds to a methylene group, and

R⁴ ' corresponds to H, CN, F or (C₁ -C₄)alkyl, or

(b) a silane of the general formula (IV) or (V) ##STR14## is reactedwith an alkylating agent of the general formula (VI) ##STR15## ifappropriate in the presence of a base, or (c) a silane of the generalformula (VII) ##STR16## is reacted with a XH-acidic compound of the type(VIII) ##STR17## in the presence of a base, or with an organometalliccompound of the type (IX) ##STR18## or (d) for compounds where X=CH₂, asilane of the general formula (X) ##STR19## is reacted with a compoundof the type (XI) ##STR20## or (e) for compounds where X=CH₂, a silane ofthe general formula (XII) ##STR21## is reacted with an organometalliccompound of the general formula (XIII) ##STR22## or (f) a silane of thegeneral formula (XIV) ##STR23## is reacted with an organometallicreagent of the type (XV)

    R.sup.1' --M                                               (XV)

in which

R^(1') has the meaning of R¹ with the exception of nitro, cyano, aminoand carbonyl-containing radicals or

(g) a silane of the general formula (XVI) ##STR24## is reacted with anorganometallic reagent of the type (XVII)

    M--R.sup.5                                                 (XVII)

or

(h) for compounds where X=CH₂, a silane of the general formula (XXX)##STR25## is reacted with an olefin of the general formula (XXXI)##STR26## in the presence of a complex of an element of subgroup VIII ofthe periodic system as catalyst or

(i) for compounds where X=CH₂, a silane of the general formula (XXXII)##STR27## is reacted with an alkylating agent of the general formula(XXXIII) ##STR28## Some of the silanes of the formula (II) to be used asstarting compounds in the preparation process (a) are novel and can beprepared, by a process which is known per se from the literature, bystarting from a silane of the general formula (XVIII), (XIX) or (XX) andintroducing the organic radicals which are still absent using suitableorganometallic reagents (see Methoden der org. Chemie [Methods ofOrganic Chemistry] (Houben-Weyl), Vol. XIII/5, Georg Thieme Verlag,Stuttgart, 1980), ##STR29## in which R, R' and R" correspond to theradicals R¹, R² and R³, and Y and M are as defined above.

Some of the organometallic reagents of the general formula (III) to beused as starting compounds in the preparation process (a) are novel andcan be prepared, by processes which are known per se from theliterature, by initially converting a carbonyl compound of the generalformula (XXI), ##STR30## in which R⁴ and R⁵ are as defined above,according to Reformatsky (see Methoden der org. Chemie [Methods ofOrganic Chemistry] (Houben-Weyl), Vol. XIII/2a, Georg Thieme Verlag,Stuttgart 1973), according to Wittig (see Methoden der org. Chemie[Methods of Organic Chemistry] (Houben-Weyl), Vol. E1, Georg ThiemeVerlag, Stuttgart 1982) or according to Horner (see L. Horner, Fortschr.Chem. Forsch. 7/1, 1 (1966/67)) to the corresponding α,β-unsaturatedester (XXII), ##STR31## in reducing this by standard methods (seeMethoden der org. Chemie [Methods of Organic Chemistry] (Houben-Weyl),Vol. 4/1c and 4/1d, Georg Thieme Verlag, Stuttgart 1980 and 1981) to thealcohol (XXIII), ##STR32## and then converting this by standard methods(see Methoden der org. Chemie [Methods of Organic Chemistry](Houben-Weyl), Vol. 5/3 and 5/4, Georg Thieme Verlag, Stuttgart, 1960and 1962) to a suitable halide (XXIV), ##STR33## which finally reactswith an alkali metal or alkaline earth metal to give the requiredorganometallic reagents of the type (III).

Some of the silanes of the general formula (IV) and (V) to be used asstarting compounds in the preparation process (b) are novel and can beprepared, by methods which are known per se from the literature (seeMethoden der org. Chemie [Methods of Organic Chemistry] (Houben-Weyl),Vol. XIII/5, Georg Thieme Verlag, Stuttgart 1980), by

(1) reacting a silane of the general formula (XXV), ##STR34## in whichR², R³ and Y are as defined above and Hal can be Br or Cl, with anorganometallic reagent of the general formula (XV),

    R.sup.1' --M                                               (XV)

then converting the intermediate of the type (VII) ##STR35## by standardmethods (see Methoden der org. Chemie [Methods of Organic Chemistry](Houben-Weyl), Vol. 13/3a, Georg Thieme Verlag, Stuttgart, 1982)to theborane (XXVI), ##STR36## and finally cleaving this, by methods which areknown from the literature (see Methoden der org. Chemie [Methods ofOrganic Chemistry] (Houben-Weyl), Vol. 13/3C, Georg Thieme Verlag,Stuttgart 1984), to form the desired compounds (IV) (X=O or S).

(2) converting a silane of the general formula (XXVII), ##STR37## inwhich Y denotes halogen or ##STR38## by methods which are known from theliterature (see Methoden der org. Chemie [Methods of Organic Chemistry](Houben-Weyl), Vol. XIII/5, Georg Thieme Verlag, Stuttgart, 1980) to thecorresponding metallated silane using an alkali metal, and then reactingwith formaldehyde, compounds of the type (IV) having X=O being obtained.

(3) reacting a silane of the general formula (XXVIII), ##STR39## inwhich R², R³ and Y are as defined above and

Hal denotes Cl or Br, with an organometallic reagent of the formula (XV)

    R.sup.1' --M                                               (XV)

and reacting the intermediate (XXIX) produced ##STR40## with an alkalimetal or alkaline earth metal, compounds of the type (V) having X=CH₂being obtained.

The silanes of the general formula (VII) ##STR41## to be used asstarting compounds in the preparation process (c) can be produced--forY=Hal--as described above by reaction of the silanes (XXV) withorganometallic reagents (XV).

The compounds (VII) having Y=sulfonate can expediently be synthesized byesterification of the alcohols of the type (IV), ##STR42## havingsulfonic acid radicals, by conventional methods (see Methoden der org.Chemie [Methods of Organic Chemistry] (Houben-Weyl), Vol. IX, GeorgThieme Verlag, Stuttgart, 1955).

Some of the silanes of the general formula (XXX) to be used as startingcompounds in the preparation process h) are novel and can be prepared bymethods which are known per se from the literature (see Methoden derorg. Chemie [Methods of Organic Chemistry] (Houben-Weyl), Vol. XIII/5,Georg Thieme Verlag, Stuttgart, 1980), by

(1) Reacting a silane of the general formula (XXXIV) ##STR43## with anorganometallic reagent of the formula (XI)

    R.sup.1' --M                                               (XI)

or

(2) Reducing a silane of the general formula II ##STR44## using metalhydrides such as, for example, sodium hydride or lithium aluminumhydride.

The olefines of the general formula (XXXI) ##STR45## to be used asstarting compounds in the preparation process (h) can be prepared bymethods which are known per se from the literature, by reacting anolefin of the general formula (XXXVa) or (XXXVb) ##STR46## with anorganometallic reagent, of the general formula (XXXVIa) or (XXXVIb)##STR47## which can be obtained from the corresponding halogen compound.Some of the compounds of the formula (XXXI) are novel. The presentinvention therefore also relates to compounds of the formula (XXXI) inwhich

R⁴ denotes H and

R⁵ denotes a radical of the formula ##STR48## R¹⁷ represents H orhalogen, where halogen particularly denotes fluorine.

Some of the metallated silanes of the general formula (XXXII) ##STR49##to be used as starting compounds in the preparation process (i) arenovel and can be prepared, by methods which are known from theliterature, from the educts (XXVII) ##STR50## in which Y' denotes Hal or##STR51## by reaction with an alkali metal. Some of the alkylatingagents (XXXIII) ##STR52## to be used as starting compounds in thepreparation process (i) are also novel and can be prepared by methodswhich are known from the literature (see, for example, Methoden der org.Chemie [Methods of Organic Chemistry](Houben-Weyl), Vol. V/3, GeorgThieme Verlag, Stuttgart, 1962), for example, for X=0, by reacting analcohol of the general formula (XXXVII) ##STR53## with a halogenatingagent such as, for example, hydrochloric acid, hydrobromic acid orthionyl chloride, in the presence of paraformaldehyde.

Some of the further compounds of the general formulae (VI), (VIII),(IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI) and (XVII) to be usedas starting compounds are also novel. They are synthesized by thesynthesis stages cited in the text above (see the literature citedabove).

The process versions (a), (d), (e), (f), (g) and (i) mentioned arepreferably carried out in a diluent whose nature depends on the type ofthe organometallic compound employed. Suitable diluents are, inparticular, aliphatic and aromatic hydrocarbons such as, for example,pentane, hexane, heptane, cyclohexane, petroleum ether, benzine,ligroine, benzene, toluene and xylene, ethers such as, for example,diethyl and dibutyl ether, glycol dimethyl ether, diglycol dimethylether, tetrahydrofurane and dioxane, and finally all possible mixturesof the abovementioned solvents.

The reaction temperature in the abovementioned process versions isbetween -75° C. and +150° C., preferably between -75° C. and +105° C.The starting materials are usually employed in equimolar amounts.However, an excess of one or other of the reaction components ispossible.

The same is essentially valid for the abovementioned process versions(b) and (c) as for versions (a) and (d)-(g). When educts of the type(IV) and (VIII) are used, however, further diluents can be employed.Thus, in these cases, ketones such as acetone, methylethyl ketone,methylisopropyl ketone and methyl isobutyl ketone, esters such as methyland ethyl acetate, nitriles such as, for example, acetonitrile andpropionitrile, amides such as, for example, dimethylformamide,dimethylacetamide and N-methylpyrrolidone, and dimethyl sulfoxide,tetramethylene sulfone and hexamethylphosphoric triamide are alsosuitable as diluents. Inorganic bases such as, for example, alkali metalor alkaline earth metal hydroxides, hydrides, carbonates orbicarbonates, but also organic bases such as, for example, pyridine,triethylamine, N,N-diisopropylethylamine or diazabicyclooctane are usedas bases.

The process version (h) mentioned is preferably carried out--in contrastto all other processes for the synthesis of compounds of the generalformula I--without diluent. However, solvents such as cyclohexane,petroleum ether, benzene, toluene, tylol and others are also suitable asreaction medium. Complex compounds of the elements of subgroup VIII ofthe periodic system, such as, for example, H₂ PtCl₆, Co₂ (CO)₈, Rh₄(CO)₁₂, Ir₄ (CO)₁₂, or RhCl[P(C₆ H₅)₃ ]₃ are used as catalysts (seeMethoden der org. Chemie [Methods of Organic Chemistry] (Houben-Weyl),Vol. XIII/5, Georg Thieme Verlag, Stuttgart, 1980, p. 51 et. seq. andthe literature cited therein). The catalyst to reacted educts ratiodepends on the type of the catalyst and, in the case of H₂ PtCl₆, forexample, varies in the range 1:10⁷ to 1:10⁶.

The compounds of the formula (I) are isolated and, if appropriate,purified by generally conventional methods, for example by evaporationof the solvent (if appropriate under reduced pressure) and subsequentdistillation or chromatography, or by distribution of the crude productbetween two phases and subsequent conventional work-up

The compounds of the general formula (I) are easily soluble in mostorganic solvents.

The active compounds are suitable for combating animal pests, inparticular insects, arachnida and nematodes, encountered in agriculture,in forestry, in the protection of stored products and of materials, andin the field hygiene, and have good plant tolerance and favourabletoxicity to warm-blooded animals. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber. From the order of theDiplopoda, for example, Blaniulus guttulatus. From the order of theChilopoda, for example, Geophilus carpophagus and Scutigera spec. Fromthe order of the Symphyla, for example, Scutigerella immaculata. Fromthe order of the Thysanura, for example, Lepisma saccharina. From theorder of the Collembola, for example, Onychiurus armatus. From the orderof the Orthoptera, for example, Blatta orientalis, Periplanetaamericana, Leucophaea maderae, Blattellagermanica, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplusdifferentialis and Schistocerca gregaria. From the order of theDermaptera, for example, Forficula auricularia. From the order of theIsoptera, for example, Reticulitermes spp.. From the order of theAnoplura, for example, Phylloxera vastatrix, Pemphigus spp. Pediculushumanus corporis, Haematopinus spp. and Linognathus spp. From the orderof the Mallophaga, for example, Trichodectes spp. and Damalinea spp.From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci. From the order of the Heteroptera, for example,Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimexlectularius, Rhodnius prolixus and Triatoma spp. From the order of theHomoptera, for example, Aleurodes brassicae, Bemisia tabaci,Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae,Cryptomyzus ribis, Doralis fabae, Doralis pomo, Eriosoma lanigerum,Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli,Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettixcincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,Pseudococcus spp. and Psylla spp. From the order of the Lepidoptera, forexample, Pectinophora gossypiella, Bupalus piniarius, Cheimatobiabrumata, Lithocolletis blancardella, Hyponomeuta padella, Plutellamaculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantriaspp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygmaexigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodopteraspp., Trichoplusiani, Caporcapsa pomonella, Pieris spp., Chilo spp.,Pyrausta nubilalis, Ephestia koehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana. From the order of the Coleoptera,for example, Anobium punctatum, Rhizopertha dominica, Bruchidiusobtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp.,Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.,Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallonsolstitialis and Costelytra zealandica. From the order of theHymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp.,Monomorium pharaonis and Vespa spp. From the order of the Diptera, forexample, Aedes spp., Anopheles spp., Culex spp , Drosophilamelanogaster, Musca spp., Fannia spp., Calliphora erythrocephala,Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp.,Hyppobosca spp., Stomoxys spp , Oestrus spp., Hypoderma spp., Tabanusspp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp. From the order of the Arachnida, for example, Scorpiomaurus and Latrodectus mactans. From the order of the Acarina, forexample, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssusgallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp.,Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.,Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The compounds furthermore have an excellent action against nematodeswhich are harmful to plants, for example against those of the generaMeloidogyne, Heterodera, Ditylenchus Aphelenchoides, Radopholus,Globodera, Pratylenchus, Longidorus and Xiphinema.

The invention also relates to agents which contain the compounds of theformula (I) in addition to suitable formulation auxiliaries.

The agents according to the invention contain the active compounds ofthe formula (I), in general to 1-95% by weight. They can be used in theconventional preparations as wettable powders, emulsifiableconcentrates, sprayable solutions, dusting agents or granulates.

Wettable powders are preparations which can be dispersed uniformly inwater and which also contain, besides the active compound and a diluentor inert substance, wetting agents, for example polyoxethylatedalkylphenols, polyoxethylated fatty alcohols or alkyl or alkylphenolsulfonates, and dispersing agents, for example sodium ligninesulfonate,sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodiumdibutylnaphthalenesulfonate or sodium oleylmethyltaurate.

Emulsifiable concentrates are prepared by dissolving the active compoundin an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene or, alternatively, higher boiling aromatics orhydrocarbons, with addition of one or more emulsifiers. Examples ofemulsifiers which may be used are: calcium salts of alkylarylsulfonicacid, such as calcium dodecylbenzenesulfonate, or non-ionic emulsifierssuch as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fattyalcohol polyglycol ethers, propylene oxide/ethylene oxide condensationproducts, alkyl polyethers, sorbitol fatty acid esters, polyoxyethylenesorbitol fatty acid esters or polyoxyethylene sorbitol esters.

Dusting agents are obtained by grinding the active compound with finelydivided solid substances, for example talc, natural clays such askaolin, bentonite, poryphillite or diatomaceous earth. Granules can beprepared either by atomizing the active compound onto absorptive,granulated inert material or by applying the active compoundconcentrates by means of adhesives, for example polyvinyl alcohol,sodium polyacrylate or, alternatively, mineral oils, onto the surface ofcarrier materials such as sand, kaolinites or granulated inert material.Suitable active compounds can also be prepared in the conventionalfashion for the preparation of fertilizer granulates--if desired as amixture with fertilizers.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates,formamidines, tin compounds and substances produced by microorganisms,inter alia. Preferred co-constituents of the mixture are

1. from the group comprising the phosphates, azinphosethyl,azinphos-methyl, 1-(4-chlorophenyl)-4-(0-ethyl,S-propyl)phosphoryloxypyrazole (TIA-230), chlorpyrifos, coumaphos,demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoat, ethoprophos,etrimfos, fenitrothion, fenthion, heptenophos, parathion,para-thionmethyl, phosalon, pirmiphos-ethyl, pirimiphos-methyl,profenfos, prothiofos, sulprofos, triazophos, trichlorphon.

2. from the group comprising the carbamates, aldicarb, bendiocarb, BPMC(2-(1-Methylpropyl)phenylmethylcarbamate), mutocarboxim, butoxicarboxim,carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl,oxamyl, primicarb, promecarb, propoxur, thiodicarb.

3. from the group comprising the carboxylates, allethrin, alphametrin,bioallethrin, bioresmethrin, cycloprothrin, cyfluthrin, cyhalothrin,cypermethrin, deltamethrin, α-cyano-3-phenyl-2-methylbenzyl2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanoate (FMC54800), fenpropathrin, fenfluthrin, fenvalerat, flucythrinate,flumethrin, fluvalinate, permethrin, resmethrin, tralomethrin.

4. From the group comprising the formamidines, amitraz, chlordimeform

5. From the group comprising the tin compounds, azocyclotin, cyhexatin,fenbutatin-oxid

6. Others α- and β-avermectins, Bacillus thuringiensis, bensultap,binapacryl, bisclofentezin, buprofecin, cartap, cyromacin, docofol,endosulfan, ethopyroxyfen, fenoxycarb, hexythiazox,3-[2-(4-Ethoxyphenyl)-2-methyl-propoxymethyl]-1,3-diphenyl ether(MTI-500), 5-[4-(4-Ethoxyphenyl)-4-methylpentyl]-2-fluoro-1,3-diphenylether (MTI-800),3-(2-Chlorophenyl)-3-hydroxy-2-(2-phenyl-4-thiazolyl)propene nitrile (SN72129), thiocyclam, nuclear polyhedroses and granuloses of viruses.

The active compound concentration of the use forms prepared from thecommercially available formulations can vary within wide ranges. Theactive compound concentration of the use forms can be between 0.0000001to 100% by weight of active compound, preferably between 0.00001 and 1%by weight.

The application occurs in a conventional fashion which is matched to themethods of use.

The active compounds according to the invention are also suitable forcombating ecto- and endoparasites, preferably ectoparasitic insects, inthe veterinary medicine field and in the field of animal husbandry.

The active compounds according to the invention are used in a knownfashion, such as by oral administration in the form of, for example,tablets, capsules, drenches or granulates, by dermal administration inthe form of, for example, dipping, spraying, pour-on, spot-on andpowdering, and by parenteral administration in the form of, for example,injection.

The novel compounds of the formula (I) according to the invention can,accordingly, also be particularly advantageously employed in cattlehusbandry (for example beef cattle, sheep, pigs and poultry such aschickens, geese etc.). In a preferred embodiment of the invention, thenovel compounds are administered orally to the animals, if appropriatein suitable formulations (cf. above) and if appropriate with thedrinking water or feed. Since excretion in the droppings occurs in aneffective manner, the development of insects in the dropping of theanimals can be prevented very simply in this fashion. The suitabledosages and formulations in each case are particularly dependent on thetype and stage of development of the productive livestock and also onthe infestation intensity of the insects, and can easily be determinedand fixed by the conventional methods. In the case of cattle, the novelcompounds may be employed, for example, in dosage amounts of 0.1 to 100mg/kg of body weight.

The following examples illustrate the invention.

A. Formulation Examples

(a) A dusting agent is obtained by mixing 10 parts by weight of activecompound and 90 parts by weight of talc as inert substance andcomminuting in an impact pulverizer.

(b) A wettable powder which can easily be dispersed in water is obtainedby mixing 25 parts by weight of active compound, 65 parts by weight ofkaolin-containing quartz as inert substance, 10 parts by weight ofpotassium ligninsulfonate and 1 part by weight of sodiumoleoylmethyltaurate as wetting and dispersing agent, and grinding in apin disc mill.

(c) A dispersion concentrate which can easily be dispersed in water isproduced by mixing 20 parts by weight of active compound with 6 parts byweight of alkylphenol polyglycol ether (®TritonX 207), 3 parts by weightof isotridecanol polyglycol ether (8 EO) and 71 parts by weight ofparaffinic mineral oil, (boiling range, for example, about 255 to above377° C.), and ground to a fineness of below 5 microns in an abrasiveball mill.

(d) An emulsifiable concentrate can be produced from 15 parts by weightof active compound, 75 parts by weight of cyclohexanone as solvent and20 parts by weight of oxethylated nonylphenol (10 EO) as emulsifier.

(e) A granulate can be produced from 2 to 15 parts by weight of activecompound and an inert granulate support material such as attapulgite,pumice granulate and/or quartz sand.

B. CHEMICAL EXAMPLES Preparation procedures

(a) 12.34 g (50 mmol) of 3-(3-phenoxyphenyl(propyl chloride are reactedwit 1.22 g (50 mmol) of magnesium in 30 ml of anhydrous ether to formthe corresponding Grignard reagent. 11.5 g (50 mmol) of a mixturecomprising dimethyl (4-ethoxyphenyl)silyl chloride (66% by weight) anddimethyl (4-ethoxyphenyl)silyl bromide (34% by weight) in 10 ml of etherare added dropwise, and the mixture is subsequently refluxed for 40 h.After cooling to 10° C., 50 ml of ice-water and 150 ml of ether areadded to the reaction mixture, which is stirred vigorously. Afterseparating off the aqueous phase, the organic layer is washedsuccessively with 50 ml of water and 50 ml of semisaturated sodiumchloride solution, dried over CaCl₂, and concentrated. The residue (19.3g 99% of theory) is distilled in a bulb tube. 15.6 g (80% of theory) ofdimethyl(4-ethoxyphenyl)-3-(3 -phenoxyphenyl)propylsilane which passesover at an oven temperature of 220°-240° C./0.1 mbar are obtained. n_(d)²².3 =1.5667.

(b) A mixture of 4.16 g (20 mmol) of 2,3,4,5,6-pentafluoroallylbenzeneand 3.79 g (21 mmol) of dimethyl(4-ethoxyphenyl)silane is treated with alittle hexachloroplatinic acid and stirred at room temperature. Afterabout 30 min, a vigorously epothermic reaction commences. After arecooling the reaction mixture, the product is purified by bulb tubedistillation. 6.71 g (86%) ofdimethyl(4-ethoxyphenyl)-(3-2,3,4,5,6-pentafluorophenyl)propylsilane areobtained as a colorless oil which passes over at an oven temperature of160°-165° C./0.2 mbar. n_(d) ²³ =1.4988.

The compound of the formula (I), where X=CH₂, listed below are preparedaccording to these procedures. The following compounds where X=O, S orNR⁶ can be prepared, for example, by process (b).

      Comp.        No. R.sup.1 R.sup.2 R.sup.3 X R.sup.4 R.sup.5 Physical     data           1      ##STR54##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR55##      n.sub.D.sup.25 = 1.5670      2     ##STR56##      CH.sub.3 CH.sub.3 O H      ##STR57##      3     ##STR58##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR59##      n.sub.D.sup.22 = 1.5621      4     ##STR60##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR61##      n.sub.D.sup.22 = 1.6042      5     ##STR62##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR63##      n.sub.D.sup.22 = 1.5480      6     ##STR64##      CH.sub.3 CH.sub.3 O H      ##STR65##      7     ##STR66##      ##STR67##      ##STR68##      CH.sub.2 H      ##STR69##      8     ##STR70##      CH.sub.3 CH.sub.3 O H      ##STR71##      9     ##STR72##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR73##      10     ##STR74##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR75##      n.sub.D.sup.32 = 1.5691  11 H.sub.3 C(CH.sub.2).sub.3 CH.sub.3 CH.sub.3     CH.sub.2 H      ##STR76##      12     ##STR77##      CH.sub.3 CH.sub.3 O H      ##STR78##      13     ##STR79##      CH.sub.3 CH.sub.3 O H      ##STR80##      14     ##STR81##      CH.sub.3 CH.sub.3 O H      ##STR82##      15     ##STR83##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR84##             16     ##STR85##      CH.sub.3 CH.sub.3 O      ##STR86##              17     ##STR87##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR88##      18     ##STR89##      CH.sub.3 CH.sub.3 O H      ##STR90##             19     ##STR91##      CH.sub.3 CH.sub.3 O      ##STR92##              20     ##STR93##      CH.sub.3 CH.sub.3 O H      ##STR94##      21     ##STR95##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR96##      22     ##STR97##      CH.sub.3 CH.sub.3 O H      ##STR98##      23     ##STR99##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR100##      n.sub.D.sup.26 = 1.5302      24     ##STR101##      CH.sub.3 CH.sub.3 O H      ##STR102##      25     ##STR103##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR104##      26     ##STR105##      CH.sub.3 CH.sub.3 O H      ##STR106##      27     ##STR107##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR108##      28     ##STR109##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR110##      n.sub.D.sup.24 = 1.5363      29     ##STR111##      CH.sub.3 CH.sub.3 O H      ##STR112##      30     ##STR113##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR114##      31     ##STR115##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR116##      n.sub.D.sup.24 = 1.5848      32     ##STR117##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR118##      33     ##STR119##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR120##      n.sub.D.sup.26 = 1.5280      34     ##STR121##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR122##      n.sub.D.sup.25 = 1.5778      35     ##STR123##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR124##      n.sub.D.sup.26 = 1.5363      36     ##STR125##      CH.sub.3 CH.sub.3 O H      ##STR126##      37     ##STR127##      CH.sub.3 CH.sub.3 O H      ##STR128##      38     ##STR129##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR130##      39     ##STR131##      CH.sub.3 CH.sub.3 O H      ##STR132##      40     ##STR133##      C.sub.2 H.sub.3 C.sub.2      H.sub.3 CH.sub.2 H     ##STR134##      n.sub.D.sup.24 = 1.5626      41     ##STR135##      CH.sub.3 CH.sub.3 O H      ##STR136##      42     ##STR137##      CH.sub.3      ##STR138##      CH.sub.2 H      ##STR139##      n.sub.D.sup.23 = 1.5839             43     ##STR140##      ##STR141##      CH.sub.2 H      ##STR142##      n.sub.D.sup.24 = 1.5749              44     ##STR143##      CH.sub.3 CH.sub.3 O H      ##STR144##      45     ##STR145##      CH.sub.3 CH.sub.3 O H      ##STR146##      46     ##STR147##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR148##             47     ##STR149##      ##STR150##      CH.sub.2 H      ##STR151##              48     ##STR152##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR153##      49     ##STR154##      CH.sub.3 CH.sub.3 O H      ##STR155##      50     ##STR156##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR157##      51     ##STR158##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR159##      n.sub.D.sup.26 = 1.5608      52     ##STR160##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR161##      n.sub.D.sup.24,5 = 1.5641      53     ##STR162##      CH.sub.3 CH.sub.3 O H      ##STR163##      54     ##STR164##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR165##      n.sub.D.sup.20 = 1.5692      55     ##STR166##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR167##      n.sub.D.sup.21 = 1.5550      56     ##STR168##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR169##      57     ##STR170##      CH.sub.3 CH.sub.3 S H      ##STR171##      58     ##STR172##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR173##      n.sub.D.sup.25 = 1.5699      59     ##STR174##      CH.sub.3 CH.sub.3 NCH.sub.3 H      ##STR175##      n.sub.D.sup.25 = 1.5667      60     ##STR176##      CH.sub.3 CHCH.sub.2 CH.sub.2 H      ##STR177##      n.sub.D.sup.25 = 1.5659      61     ##STR178##      CH.sub.3 n-C.sub.3      H.sub.7 CH.sub.2 H     ##STR179##      n.sub.D.sup.24 = 1.5603      62     ##STR180##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR181##      n.sub.D.sup.25 = 1.5891      63     ##STR182##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR183##      n.sub. D.sup.24 = 1.5492             64     ##STR184##      ##STR185##      CH.sub.2 H      ##STR186##              65     ##STR187##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR188##      n.sub.D.sup.24 = 1.5796      66     ##STR189##      CH.sub.3 C.sub.2      H.sub.3 CH.sub.2 H     ##STR190##      n.sub.D.sup.23 = 1.5614      67     ##STR191##      CH.sub.3 CH.sub.3 O H      ##STR192##      68     ##STR193##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR194##      n.sub.D.sup.22,3 = 1.5667      69     ##STR195##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR196##      70     ##STR197##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR198##      n.sub.D.sup.26 = 1.5669      71     ##STR199##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR200##      72     ##STR201##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR202##      n.sub.D.sup.25 = 1.5691             73     ##STR203##      CH.sub.3 CH.sub.3 O      ##STR204##              74     ##STR205##      CH.sub.3 CH.sub.3 O H      ##STR206##      75     ##STR207##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR208##      n.sub.D.sup.22 = 1.5940      76     ##STR209##      CH.sub.3 CH.sub.3 O H      ##STR210##      77     ##STR211##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR212##      78     ##STR213##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR214##      n.sub.D.sup.26 = 1.5838  79 (H.sub.3 C).sub.2 CH CH.sub.3 CH.sub.3     CH.sub.2 H      ##STR215##      80     ##STR216##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR217##             81     ##STR218##      CH.sub.3 CH.sub.3 O      ##STR219##              82     ##STR220##      CH.sub.3 CH.sub.3 O H      ##STR221##      83     ##STR222##      CH.sub.3 CH.sub.3 O H      ##STR223##      84     ##STR224##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR225##      85     ##STR226##      CH.sub.3 CH.sub. 3 CH.sub.2 H      ##STR227##      n.sub.D.sup.25 = 1.5462      86     ##STR228##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR229##      n.sub.D.sup.24 = 1.5650      87     ##STR230##      CH.sub.3 CH.sub.3 O H      ##STR231##      88     ##STR232##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR233##      89     ##STR234##      CH.sub.3 CH.sub.3 NCH.sub.3 H      ##STR235##      90     ##STR236##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR237##      n.sub.D.sup.26 = 1.5620      91     ##STR238##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR239##      n.sub.D.sup.24 = 1.5573      92     ##STR240##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR241##      93     ##STR242##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR243##      n.sub.D.sup.23 : 1,4988      94     ##STR244##      CH.sub. 3 CH.sub.3 O H      ##STR245##      95     ##STR246##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR247##      96     ##STR248##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR249##      97     ##STR250##      CH.sub.3 CH.sub.3 O H      ##STR251##      98     ##STR252##      CH.sub.3 CH.sub.3 O H      ##STR253##      99     ##STR254##      CH.sub.3 CH.sub.3 O H      ##STR255##      100     ##STR256##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR257##      n.sub.D.sup.19 = 1.5623      101     ##STR258##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR259##      102     ##STR260##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR261##      103     ##STR262##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR263##      n.sub.D.sup.24 = 1.5388      104     ##STR264##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR265##      n.sub.D.sup.26 = 1.5731      105     ##STR266##      CH.sub.3 CH.sub.3 NC.sub.2      H.sub.3 H     ##STR267##      n.sub.D.sup.25 = 1.5595      106     ##STR268##      CH.sub.3 CH.sub.3 O H      ##STR269##      107     ##STR270##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR271##      108     ##STR272##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR273##      109     ##STR274##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR275##      n.sub.D.sup.22 = 1.5751  110 H.sub.3 C.sub.2 CH.sub.3 CH.sub.3 CH.sub.2     H      ##STR276##      111     ##STR277##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR278##      112     ##STR279##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR280##      n.sub.D.sup.22 = 1.5778      113     ##STR281##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR282##      114     ##STR283##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR284##      n.sub.D.sup.20 = 1.5879      115     ##STR285##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR286##      116     ##STR287##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR288##      n.sub.D.sup.22 = 1.5740      117     ##STR289##      CH.sub.3 CH.sub.3 S H      ##STR290##       118 (H.sub.3 C).sub.3 CCH.sub.2CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR291##      119     ##STR292##      CH.sub.3 CH.sub.3 O CH.sub.3      ##STR293##      120     ##STR294##      CH.sub.3 CH.sub.3 O CH.sub.3      ##STR295##      121     ##STR296##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR297##      n.sub.D.sup.32 = 1.5150      122     ##STR298##      CH.sub.3 CH.sub.3 O H      ##STR299##      123     ##STR300##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR301##      n.sub.D.sup.23 = 1.5842      124     ##STR302##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR303##      n.sub.D.sup.25 = 1.5401      125     ##STR304##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR305##      126     ##STR306##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR307##      127     ##STR308##      CH.sub.3 CH.sub.3 O CCH      ##STR309##      128     ##STR310##      CH.sub.3 CH.sub.3 CH.sub.2 CN      ##STR311##      129     ##STR312##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR313##      130     ##STR314##      CH.sub.3 CH.sub.3 CH.sub.2 H      ##STR315##      131     ##STR316##      CH.sub.3 CH.sub.3 CH.sub.2 H "      132     ##STR317##      CH.sub.3 CH.sub.3 CH.sub.2 F      ##STR318##      133     ##STR319##      CH.sub.3 CH.sub.3 CH.sub.2 F      ##STR320##      134 "  CH.sub.3 CH.sub.3 CH.sub.2 F     ##STR321##      135 " CH.sub.3 CH.sub.3 CH.sub.2 F     ##STR322##      136 " CH.sub.3 CH.sub.3 CH.sub.2 H     ##STR323##      137 " CH.sub.3 CH.sub.3 CH.sub.2 H     ##STR324##      138 " CH.sub.3 CH.sub.3 CH.sub.2 H     ##STR325##

C. BIOLOGICAL EXAMPLES Example 1

Field beans (Vicia faba) which were heavily infested with Cowpea aphid(Aphis craccivora) were sprayed with aqueous dilutions of emulsionconcentrates containing 1000 ppm of active compound until the stagewhere dripping commenced. After 3 days, the mortality was 100% in eachcase for the preparations containing the active compounds of Examples 5,33, 51, 54, 55, 68, 70, 75, 85, 86, 90, 112 and 114.

Example 2

Bean plants (Phaseolus vulgaris) which were heavily infested withgreenhouse whitefly (Trialeurodes vaporarium) were sprayed with aqueousdilutions of emulsion concentrates (1000 ppm of active compound) untildripping commenced. 14 days after the plants were placed in agreenhouse, they were inspected microscopically, with a result of 100%mortality in each case of the preparations containing the activecompound of Examples 33, 54, 55, 68, 90 and 104.

Example 3

Experimental procedure: analogous to Example 2

Experimental animals: Tetranychus urticae (two-spotted spider mite)

Experimental plants: Phaseolus vulgaris (kidney bean)

Amount applied: 1000 ppm of active compound in the spray liquid

After 8 days, an activity of 100% mortality was observed for compound33.

Example 4

Bean plants (Phaseolus vulgaris) were heavily infested with citrusmealybug (Pseudococcus citri) were sprayed with aqueous dilutions ofemulsion concentrates (1000 ppm of active compound in the spray liquidin each case) until the stage where dripping commenced.

After standing for 7 days in a greenhouse at 20°-25° C., the inspectionwas carried out. 100% mortality was determined for the compoundsaccording to Examples 5, 33, 51, 54, 55, 68, 70, 75, 85, 86, 90, 112 and114.

Example 5

Milkweed bugs (Oncopeltus fasciatus) were treated with aqueous dilutionsof emulsion concentrates (1000 ppm of active compound in the sprayliquid in each case) of the active compounds of Examples 5, 33, 51, 54,55, 68, 70, 75, 85, 86, 90, 112 and 114.

The bugs were subsequently placed at room temperature in containersprovided with lids which were permeable to air. 5 days after thetreatment, the mortality was determined and was 100% in each individualcase.

Example 6

The insides of the bases of Petri dishes coated with a syntheticnutrient medium were sprayed, after solidification of the feedstuffpaste, in each case with 3 ml of an aqueous emulsion containing 2000 ppmof active compound. After the spray coating had dried and 10 larvae ofthe common cotton worm (Prodenia litura) were inserted, the dishes werestored for 7 days at 21° C. and the degree of action of the respectivecompound (expressed in % mortality) was determined. The compounds 5, 33,51, 54, 55, 68, 70, 85, 86, 90, 100, 104, 112 and 114 produced anactivity of 100% in each case in this test.

Example 7

Bean leaves (Phaseolus vulgaris) were treated with an aqueous emulsionof the compound of Example 68 in a concentration of 1000 ppm (based onthe active compound) and placed with similarly treated larvae of theMexican bean beetle (Epilachna varivestis) in observation cages. Anevaluation of the 48 hours showed 100% destruction of the experimentalanimals. The compounds according to Examples 33, 51, 55 and 70 provedsimilarly effective.

Example 8

1ml of Example 68 as active compound in acetone with a concentration of1000 ppm was applied evenly to the inside of the lid and the base of aPetri dish using a pipette, and the dish was left open until the solventhad evaporated completely. 10 houseflies (Musca domestica) were thenplaced in the Petri dishes, the dishes were closed using the lid, and a100% destruction of the experimental animals was determined after 3hours. The compounds according to Examples 5, 33, 51, 55, 70 and 86 alsoproved effective.

Example 9

1 ml of an active compound solution in acetone having a concentration of2000 ppm was applied evenly to the inside of the lid and the base of aPetri dish using a pipette. After the solvent had evaporated completely,10 Larvae (L4) of the German cockroach (Blatella germanica) wereinserted into each Petri dish, and the dishes were closed using thelids. After 72 hours, the action (expressed in % mortality) wasdetermined. The compounds 1, 3, 5, 28, 33, 51, 54, 55, 68, 70, 75, 85,86, 100, 112 and 114 gave an activity of 100% in each case in this test.

We claim:
 1. A compound of the formula ##STR326## wherein R⁴ is H, R⁵ isa radical of the ##STR327## and R¹⁷ is halogen.
 2. The compound of claim1 wherein R¹⁷ is fluorine.
 3. A compound of formula ##STR328## whereinR⁴ is hydrogen and R⁵ is a radical of the formula ##STR329##
 4. Acompound of the formula ##STR330## wherein R⁴ is H, R⁵ is a radical ofthe formula ##STR331## and R¹⁷ is hydrogen or halogen.
 5. The compoundof claim 4 wherein R¹⁷ is fluorine.